CN101688103A - Adhesive, composite material containing the same, and method for producing composite material - Google Patents

Abstract

The present invention provides an adhesive that does not react during the accumulation of composite material raw materials after application of the adhesive, yet exhibits rapid temperature sensitivity during curing during hot press molding. Furthermore, a composite material (particularly a sheet) containing the adhesive and exhibiting excellent productivity, secondary workability, water absorption expansion coefficient, flexural modulus, and peel strength, and a method for producing the same are provided. The adhesive is characterized in that it comprises a first component and a second component, wherein the first component comprises 100 parts by weight of a polyol (a) having a weight-average molecular weight of 150 to 4000 and containing no nitrogen atoms, and 0.5 to 65 parts by weight of a compound (b) having a nitrogen atom per 100 parts by weight of the polyol (a), and the second component comprises an organic isocyanate compound, wherein at least one mixture of the first and second components, wherein the total amount of (a) and (b) in the first component is 2 to 35 parts by weight relative to 100 parts by weight of the organic isocyanate compound in the second component, satisfies certain specific conditions as measured in accordance with JIS K6807.

Description

Adhesive, composite material containing same, and method for producing composite material

technical field

The invention relates to an adhesive, a composite material containing the adhesive and a method for manufacturing the composite material. The adhesive contains a polyhydric alcohol without a nitrogen atom, a compound with a nitrogen atom, and an organic isocyanate compound. Easily adjust curing time. In particular, it relates to a binder suitable for thermocompression molding of a composite material, a composite material containing the binder, and a method for producing the composite material.

Background technique

It has been used as particle board, waffle board, OSB (oriented strand board), insulation board (insulation board), hard board, medium density fiber board (Medium Density Fiber Board) or obtained by molding rice husk Rice husk boards or sorghum boards obtained by molding sorghum stalks, such as boards obtained by using lignocellulose or grains, and inorganic boards made of inorganic materials as raw materials (hereinafter, they are also collectively referred to as boards) As adhesives or adhesives for compression molding, thermosetting urea resins, melamine resins, urea melamine resins, melamine urea resins, phenolic resins, and melamine phenolic resins are widely used (hereinafter, the above resins are also referred to as formaldehyde-based adhesives). wait. The formaldehyde-based adhesive is inexpensive, has excellent adhesive force, and is cured in a relatively short period of time. However, formaldehyde released from products molded with the above-mentioned formaldehyde-based binder is regarded as an environmental problem. As a current countermeasure, when compounding a formaldehyde-based adhesive, add a formaldehyde scavenger or the like to reduce the amount of formaldehyde released. However, the above-mentioned countermeasures not only increase the burden on the manufacturing process, but also are not necessarily perfect in terms of effectiveness.

On the other hand, as another countermeasure, the use of non-formaldehyde-based adhesives has been studied. For example, isocyanate-based adhesives have been proposed as adhesives for hot press molding of boards (Patent Document 1). However, if an isocyanate-based adhesive is used for thermocompression molding, the isocyanate-based adhesive adheres to the surface of the hot plate due to its excellent excessive adhesiveness. Therefore, not only does it take a lot of labor to remove the deposits, but also the bonded molded product is damaged and loses its value as a commodity. In view of the above-mentioned problems, as a compounding component of an isocyanate-based adhesive, in order to improve the releasability from a metal hot plate, for example, the following release agent composition has been proposed: a wax having a certain range of melting points and a certain amount of an emulsifier. Adhesive composition with molecular weight range (Patent Document 2), fluorophosphate ester and silicon compound (Patent Document 3), emulsified silicone oil containing polysiloxane (Patent Document 4), etc.

However, in order to obtain sufficient effects from the above measures, it is necessary to add a large amount of wax or a mold release agent, resulting in a decrease in water resistance and a decrease in physical properties of the molded article. Furthermore, by adding or coating a large amount of wax or release agent, hydrophobic components remain on the surface of the finished product, so the wettability of the surface of the finished board is reduced, and secondary processing applications become difficult.

In addition, as an accelerator for improving the physical strength of the board, and its reactive compound or catalyst, an isocyanurate catalyst (Patent Document 5), a polyoxyalkylene polyamine and a ketone compound as main components have been proposed. Curable composition (patent document 6), urethanization reaction catalyst (patent document 7), urethane prepolymer (patent document 8, 9), etc.

Although the physical strength of the sheet molding is indeed improved by the accelerator, it is difficult to adjust the reactivity. In addition, for the curable composition and urethanization reaction catalyst mainly composed of polyoxyalkylene polyamine and ketone compound, the fibers or chips after adhesive coating are placed on the former. The reaction proceeds even during middle stacking, and it is difficult to obtain the physical strength of the plate after molding. Furthermore, it is also difficult to adjust the reactivity of isocyanate after prepolymerization.

In any of the above countermeasures, there are various problems, and it is substantially difficult to adjust the hot press molding time at the production site of the board. Therefore, the actual situation is that technology that can satisfy the current situation has not been established yet.

Patent Document 1: Japanese Patent Application Laid-Open No. 58-036430

Patent Document 2: Japanese Patent Laid-Open No. 2002-194321

Patent Document 3: Japanese Patent Laid-Open No. 2002-086456

Patent Document 4: Japanese Patent Laid-Open No. 2002-248630

Patent Document 5: Japanese Patent Laid-Open No. 2003-276011

Patent Document 6: Japanese Patent Laid-Open No. 2001-151844

Patent Document 7: Japanese Patent Application Laid-Open No. 05-025133

Patent Document 8: Japanese Patent Application Laid-Open No. 06-172706

Patent Document 9: Japanese Patent Application Laid-Open No. 09-235540

Contents of the invention

The object of the present invention is to provide an adhesive that is a non-formaldehyde adhesive with little environmental load and does not react during the accumulation of raw materials for composite materials after adhesive coating. , with rapid temperature sensitivity in curing during thermocompression molding. Also provided are a composite material (particularly a board) having the adhesive which is excellent in productivity, secondary processability, water expansion ratio, flexural modulus, and peel strength, and a method for producing the same.

In order to solve the above-mentioned problems, the inventors of the present invention have studied intensively, and found that an adhesive comprising a first agent composed of a unique polyol and a compound having a nitrogen atom and a second agent composed of an organic isocyanate compound has the following properties: The temperature sensitivity of slow curing time at 60°C and fast curing time at a temperature of 110°C led to the completion of the present invention.

That is, the present invention is specified by the following matters.

The adhesive of the present invention is characterized in that the adhesive is composed of a first agent and a second agent, and the first agent contains 100 parts by weight of a polyhydric alcohol (a ), and relative to 100 parts by weight of the polyol (a), 0.5 to 65 parts by weight of a compound (b) with a nitrogen atom, the second agent contains an organic isocyanate compound; and to meet the requirements relative to the second agent The total amount of the above-mentioned (a) and (b) in the first agent is 2 to 35 parts by weight in 100 parts by weight of the organic isocyanate compound. Using at least one mixture obtained by the first agent and the second agent, according to JIS K6807 The value obtained by dividing the curing time at 60°C measured by the gelation time test method (Method A) by the curing time at 110°C measured in accordance with the gelation time test method (A method) of JIS K6807 is 30 or more, and the curing time at 60°C is 1 hour or more.

In addition, the above-mentioned first agent may only be composed of 100 parts by weight of a polyol (a) with a weight average molecular weight of 150 to 4000 that does not contain nitrogen atoms and 0.5 to 65 parts by weight of a nitrogen-containing polyol (a) relative to 100 parts by weight of the polyol (a). atomic compound (b), and the second agent may be composed only of organic isocyanate compounds.

The above-mentioned binder is also preferably, the above-mentioned (a) in the above-mentioned first agent is a polyether polyol and/or a polyester polyol not containing a nitrogen atom, and the above-mentioned (b) is made of a polyether polyol containing a nitrogen atom Polyol and/or polyester polyol (b-1) containing nitrogen atoms and amine compound (b-2), containing 0 to 50 parts by weight of (b-1) and 0.5 to 100 parts by weight of (a) 15.0 parts by weight (b-2).

The composite material of the present invention is characterized in that it is obtained by thermocompression molding a mixture containing the above-mentioned binder and an inorganic material and/or a lignocellulose material.

The method for producing a composite material according to the invention of the present application is characterized in that the above-mentioned binder and an inorganic material and/or lignocellulose material are mixed and thermocompressed.

The above manufacturing method can also use a release agent.

In the above production method, it is preferable that the temperature of the above hot press molding is in the range of 90 to 220°C.

The above-mentioned production method is also preferably that the inorganic material and/or lignocellulosic material is in the form of chips, plates, strands, flakes, finely pulverized powders or fibers. , or a mixture of them.

The adhesive of the present invention does not react during the accumulation of raw materials for composite materials after the adhesive is applied. On the other hand, it has rapid curing properties during thermocompression molding, so the curing of the adhesive can be easily adjusted. time. In addition, by using a binder having the above-mentioned temperature sensitivity, especially for inorganic materials and lignocellulose materials, it is possible to easily adjust the thermocompression bonding time, so it is possible to provide improved productivity of composite materials such as boards, and complete production High-quality composite materials with excellent secondary processability, water expansion rate, flexural modulus, and peel strength.

Detailed ways

Next, the adhesive of the present invention, a composite material using the adhesive, and a manufacturing method thereof will be described in detail.

The adhesive of the present invention consists of a first agent and a second agent. In addition, the so-called adhesive in the present invention includes both adhesive and binder.

"Dose 1"

The first agent of the present invention contains the following (a) and the following (b).

(a) Polyhydric alcohols not having nitrogen atoms

(b) Compounds with nitrogen atoms

<(a) Polyol having no nitrogen atom>

It is preferable that the weight average molecular weight of the polyol (a) which does not have a nitrogen atom is 150-4000. More preferably, it is 250-3000. When the weight average molecular weight is small, it is difficult to obtain water resistance and physical strength of the composite material when the composite material is thermocompressed; when the molecular weight is large, there is a tendency for the mixture with the second agent described below to become soft, and it is difficult to obtain the physical strength of the composite material. It should be noted that the weight average molecular weight can use the hydroxyl value (OHV) of polyether and/or polyester polyol and the functional group number (f) of the initiator when making polyether and/or polyester polyol by formula (1 ) to obtain.

Weight average molecular weight=56,100×f/OHV...(1)

The hydroxyl value (OHV) in the above formula (1) is measured according to the plastics-polyurethane raw material polyol test method of JIS K-1557-1. The unit of the obtained hydroxyl value (OHV) is represented by mgKOH/g. The number of functional groups (f) in the above formula (1) is the number of hydroxyl groups of polyhydric alcohols with hydroxyl groups. For example, the number of functional groups (f) of ethylene glycol and propylene glycol uses f=2, sucrose uses f=8, and sorbitol uses f =6, f=4 for pentaerythritol, f=3 for trimethylolpropane and glycerin. "56,100" in the above formula (1) is represented by mgKOH/g which is the same unit as the hydroxyl value (OHV), and is obtained by multiplying the molecular weight of KOH 56.1 by 1,000 in order to convert the g unit into mg unit. The weight average molecular weight is calculated|required from said Formula (1) below.

[Polyether polyol having no nitrogen atom and/or polyester polyol not having nitrogen atom]

The above-mentioned polyol (a) not having a nitrogen atom is preferably any of the following substances, 1) a polyether polyol not having a nitrogen atom, 2) a polyester polyol not having a nitrogen atom, 3) not having A mixture of polyether polyols with nitrogen atoms and polyester polyols without nitrogen atoms.

The above-mentioned polyether polyol having no nitrogen atom can be obtained by a usual polyol production method. The production method is not particularly limited, and it can be produced by adding a cyclic ether to a compound (polyol) having a hydroxyl group. It is also possible to use polyether polyols obtained by addition of one or more types of compounds (polyols) having hydroxyl groups and cyclic ethers. It will not specifically limit if it is a polyether polyol which does not have a nitrogen atom.

Examples of the compound (polyhydric alcohol) having a hydroxyl group include ethylene glycol, diethylene glycol, propylene glycol, pentaerythritol, trimethylolpropane, glycerol, sorbitol, polypropylene glycol, diethylene glycol, polyethylene glycol , butylene glycol, hexanetriol, sucrose, butylene glycol, dihydroxydiphenylpropane, sucrose, dipropylene glycol, dihydroxydiphenylpropane, dihydroxydiphenyl ether, dihydroxydiphenylmethane, Dihydroxybiphenyl, hydroquinone, naphthalenediol, resorcinol, phloroglucin and the like. Among them, ethylene glycol, propylene glycol, sucrose, sorbitol, pentaerythritol, trimethylolpropane, and glycerol are preferable, and ethylene glycol and sorbitol are more preferable from the viewpoint of reactivity with organic isocyanate compounds and adhesiveness. , pentaerythritol, trimethylolpropane, glycerol.

Moreover, as a cyclic ether, ethylene oxide, a propylene oxide, a styrene oxide, a butylene oxide, etc. are mentioned, for example. Among them, ethylene oxide and propylene oxide are preferable from the viewpoint of reactivity with organic isocyanate compounds and adhesiveness.

The above-mentioned polyester polyol having no nitrogen atom can also be obtained by a normal polyester polyol production method. It does not specifically limit about a manufacturing method, It can manufacture by making the compound (polyhydric alcohol) which has a hydroxyl group, and the compound (polyacid) which have a carboxyl group react.

Examples of the compound (polyol) having a hydroxyl group include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-propylene glycol, 1,3- or 1,4-butane Diol, neopentyl glycol, 1,6-hexanediol, 1,10-decanediol, propylene oxide and/or ethylene oxide adducts of bisphenol A, propylene oxide and bisphenol F /or ethylene oxide adducts, terephthalenedimethanol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, glycerol, trimethylolpropane, hexanetriol, pentaerythritol Alkylene oxide adducts, etc. Among these, ethylene glycol, propylene glycol, propylene oxide and/or ethylene oxide adducts of bisphenol A, propylene oxide and/or ethylene oxide adducts of bisphenol F are preferable from the viewpoint of reactivity with organic isocyanate compounds. Ethylene oxide adducts, alkylene oxide adducts of pentaerythritol, more preferably ethylene glycol, propylene oxide and/or ethylene oxide adducts of bisphenol A, and alkylene oxide adducts of pentaerythritol. The above-mentioned substances may be used alone or in combination of two or more.

In addition, examples of the compound (polyacid) having a carboxyl group include adipic acid, pimelic acid, sebacic acid, azelaic acid, maleic acid, itaconic acid, fumaric acid, phthalic acid, terephthalic acid, Dicarboxylic acid, malonic acid, succinic acid, glutaric acid, oxalic acid, isophthalic acid, hexahydrophthalic acid, fatty acids such as castor oil, or products obtained by esterifying fatty acids such as castor oil, etc. In addition, cyclic esters such as propiolactone, butyrolactone, and caprolactone, etc. can also be used. The above-mentioned substances may be used alone or in combination of two or more.

The aforementioned polyester polyol having no nitrogen atom can be obtained from the aforementioned polyether polyol and the aforementioned cyclic ester. Furthermore, it can also be used together with the said polyether polyol which does not have a nitrogen atom.

As the polyol (a) not having nitrogen, by using a polyether polyol having a weight average molecular weight of 150 to 4000, the dispersibility when applied to an inorganic material and/or a lignocellulose material is good, and by using only a polyether polyol The ether polyol increases the value of the following numerical value (T ₆₀ /T ₁₀₀ ), and an adhesive having better bulk tolerance and adhesiveness can be obtained.

<(b) Compounds having a nitrogen atom>

In the first agent of the adhesive of the present invention, 0.5 to 65 parts by weight, preferably 1 to 50 parts by weight, of the compound (b) having a nitrogen atom is contained with respect to 100 parts by weight of the polyol (a) having no nitrogen atom , More preferably 2 to 40 parts by weight.

When the compound (b) is too small, the curing time of the innermost core layer at a temperature of 110° C. during hot press molding becomes slow, and the molding time of the composite material increases, resulting in insufficient productivity. In addition, when the compound (b) is too much, the curing time at 60°C is less than 1 hour, and the stacking tolerance is insufficient. At the same time, since the reaction proceeds at room temperature, it is difficult to obtain a composite material obtained after hot press molding. physical strength.

Furthermore, when the compound (b) is composed of the following compound (b-1) and the following compound (b-2), the curing time of the adhesive at a low temperature of 60°C can be increased, and the curing time at 110°C can be shortened, so preferred.

(b-1) Any one selected from a polyether polyol having a nitrogen atom, a polyester polyol having a nitrogen atom, or a mixture of a polyether polyol having a nitrogen atom and a polyester polyol having a nitrogen atom .

(b-2) Amine compound

For compound (b-1) and compound (b-2), relative to 100 parts by weight of polyol (a), (b-1) contains 0 to 50 parts by weight, preferably 0 to 40 parts by weight, more preferably 0 -30 parts by weight, and 0.5 to 15.0 parts by weight of (b-2), preferably 1 to 10 parts by weight, more preferably 3 to 10 parts by weight, based on 100 parts by weight of the polyol (a). When (b-1) exceeds 50 parts by weight with respect to 100 parts by weight of (a), the reaction is likely to proceed at room temperature, the curing time at 60°C is less than 1 hour, and the accumulation tolerance of chips is insufficient. , At the same time, the reaction also proceeds at room temperature, so it is difficult to obtain the physical strength of the composite material after hot pressing. In addition, when (b-2) is less than 0.5 parts by weight with respect to 100 parts by weight of (a), the curing time at 110° C. becomes slow, the molding time of the composite material increases, and the productivity is insufficient. When (b-2) exceeds 15.0 parts by weight, the reaction time at 60°C becomes short, the curing time at 60°C becomes less than 1 hour, and the accumulation tolerance of chips is insufficient. The reaction is carried out, so it is difficult to obtain the physical strength of the composite material after thermocompression molding.

[(b-1) Polyether polyol having nitrogen atom and/or polyester polyol having nitrogen atom]

It is preferable that the weight average molecular weight of the said polyether polyol which has a nitrogen atom or the polyester polyol which has a nitrogen atom is 270-4000. More preferably, it is 300-3000. When the weight-average molecular weight of any polyol is small, it is difficult to obtain water resistance and physical strength of the composite material when thermocompressing the composite material. When the weight-average molecular weight is large, the mixture with the second agent described later tends to be soft, making it difficult to obtain physical strength of the composite material.

The polyether polyol having a nitrogen atom can be obtained by a usual polyether polyol production method, and the production method is not particularly limited. Specific examples of the initiator include ethanolamines such as monoethanolamine, diethanolamine, and triethanolamine, ethylenediamine, diethylenetriamine, o-toluenediamine, m-toluenediamine, 4,4'-diamino Amines such as diphenylmethane, 2,4'-diaminodiphenylmethane, polymethylpolyphenylpolyamine, aniline, etc. Among them, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, m-toluenediamine, polymethylpolyphenylpolyamine, and aniline are preferred in terms of reactivity as a binder. Diethanolamine, Triethanolamine, Ethylenediamine, Diethylenetriamine, Aniline. Polyether polyols having nitrogen atoms can be obtained by further adding polyethylene oxide, propylene oxide, butylene oxide, and the like.

The polyether polyol obtained by the above polyaddition can be used alone or in combination of two or more.

Moreover, the polyester polyol which has a nitrogen atom can also be obtained by the manufacturing method of the usual polyester polyol, The manufacturing method is not specifically limited. It can be produced by using the aforementioned ethanolamines or amines as an initiator, and reacting the aforementioned compound (polyhydric alcohol) having a hydroxyl group with the following compound (polyacid) having a carboxyl group. In addition, the obtained polyester polyol which has a nitrogen atom can be used individually or in combination of 2 or more types. In addition, it can also be used together with the above-mentioned polyether polyol having a nitrogen atom.

As the compound (polyacid) having a carboxyl group, in view of reactivity as a binder, specifically, adipic acid, maleic acid, succinic acid, isophthalic acid, malonic acid, sebacic acid, Pimelic acid, hexahydrophthalic acid, fumaric acid, more preferably adipic acid, maleic acid, succinic acid, isophthalic acid, sebacic acid, pimelic acid, fumaric acid.

[(b-2) Amine compound]

The molecular weight of the amine compound (b-2) is preferably less than 270. From the viewpoint of shortening the curing time at 110°C, it is more preferably less than 250. When the molecular weight exceeds 270, the curing time at 110° C. after mixing with the second agent described below becomes slow, and it becomes difficult to obtain the physical strength of the composite material after thermocompression molding.

Examples of the amine compound (b-2) include allylamines such as allylamine, diallylamine, and triallylamine; propylamine, methylaminopropylamine, and 2-ethylhexyloxypropylamine; , 3-Ethoxypropylamine, Dimethylaminopropylamine, Dibutylaminopropylamine, Diethylaminopropylamine, Methyliminobispropylamine, 3-Methoxypropylamine, Hydroxypropylamine, Isopropylamine, Diisopropylamine, etc. Propylamines; monoethanolamine, diethanolamine, triethanolamine, diethylethanolamine, dimethylethanolamine, 2-aminoethylethanolamine, methyldiethanolamine, dibutylethanolamine, methylethanolamine, dimethylaminoethanol, dimethylethanolamine Amino alcohols such as aminoethoxyethanol and trimethylaminoethylethanolamine; ethylamines such as ethylamine, diethylamine, triethylamine, ethylhexylamine and diethylhexylamine; dioctylamine, tetramethyl Ethylenediamine, trioctylamine, diisobutylamine, butylamine, bis(dimethylaminoethyl)ether, tris(dimethylaminomethyl)phenol, pentaethylenehexamine, dimethylcyclohexylamine , dimethylmethanolamine, N-ethylmorpholine, N, N'-dimethylpiperazine, 1,5-pentamethylenediethylenetriamine, triethylamine, tetramethylpropylenediamine, Tetramethylhexamethylenediamine, pentamethyldipropylenetriamine, 1,1,3,3-tetramethylguanidine, triethylenediamine, methylethylpiperazine, N-methylmorpholine, Dimethylaminoethylmorpholine, dimethylimidazole, methylhydroxyethylpiperazine, hydroxyethylmorpholine, ethylene glycol bis(dimethyl)aminopropyl ether, ammonia water, etc. Among them, allylamine, monoethanolamine, diethanolamine, triethanolamine, diethylethanolamine, dimethylethanolamine, methyldiethanolamine, methylethanolamine, dimethylaminoethanol, Ethylamine, diethylamine, tetramethylethylenediamine, bis(dimethylaminoethyl)ether, tris(dimethylaminomethyl)phenol, pentaethylenehexamine, dimethylcyclohexylamine, 1, 5-pentylenediethylenetriamine, triethylamine, triethylenediamine, methylethylpiperazine, more preferably triethanolamine, diethylethanolamine, dimethylethanolamine, methyldiethanolamine, methyl Ethanolamine, ethylamine, diethylamine, bis(dimethylaminoethyl)ether, tris(dimethylaminomethyl)phenol, pentaethylenehexamine, dimethylcyclohexylamine, 1,5-pentamethylene Diethylenetriamine, triethylamine, triethylenediamine. In addition, the said amine compound (b-2) can be used individually or in combination of 2 or more types, respectively.

The polyol (a) which does not have a nitrogen atom of the first agent, the polyether polyol which has a nitrogen atom and/or the polyester polyol (b-1) which has a nitrogen atom with the compound (b) which has a nitrogen atom, and The amine compounds (b-2) may be used separately or pre-mixed, but it is preferable to use a pre-mixed product in consideration of handleability.

In addition, when using the product obtained by mixing the polyol (a) and the compound (b) having a nitrogen atom in advance as the first agent, it is preferable to use the mixed solution as it is, and in consideration of the dispersibility of the first agent, it is more preferable to use the product prepared in advance. It is a product obtained by dispersing it in water such as distilled water. However, when using a product obtained by water dispersion in advance, it can be used as it is in a uniformly dispersed state, but when the aqueous dispersion is separated and the dispersion state is poor, it is preferably used after mixing uniformly before use.

However, when the dispersion state is poor and the ratio of the components as the first agent cannot be maintained, it is not preferable to use after remixing.

In the present invention, the first agent is preferably composed only of a polyol (a) having a weight average molecular weight of 150 to 4000 without a nitrogen atom and a compound (b) having a nitrogen atom, but the first agent may contain a solvent or disperse Medium, additives and other components. Examples of other components include UV absorbers, antioxidants, plasticizers, silane coupling agents, metal catalysts, waterproofing agents, defoamers, curing accelerators, mold release agents, mold release aids, tackifiers, Formaldehyde trapping agent, crosslinking agent, stabilizer, etc. Other components are not particularly limited, but can be used in a ratio of 5 parts by weight or less with respect to a total of 100 parts by weight of (a) and (b) as the amount used.

"Dose 2"

The second agent of the present invention contains an organic isocyanate compound. The organic isocyanate compound is not particularly limited as long as it is a compound having an isocyanate group that is generally used in the production of polyurethane or the like. For example, aliphatic polyisocyanate, alicyclic polyisocyanate, araliphatic polyisocyanate, aromatic polyisocyanate, derivatives and modified products of the above-mentioned polyisocyanate, etc. are mentioned.

Examples of aliphatic polyisocyanates include:

1,3-propylene diisocyanate, 1,4-butylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2 -Butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethyl 1,6-hexamethylene diisocyanate, 2, Aliphatic diisocyanates such as 6-diisocyanatomethylhexanoate;

Lysine ester triisocyanate, 1,4,8-octane triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanato-4-isocyanatomethyl octane, 1 , 3,6-hexane triisocyanate, 3,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane and other aliphatic triisocyanates.

Examples of alicyclic polyisocyanates include:

1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl Isocyanate (hereinafter also referred to as isophorone diisocyanate), 4,4'-methylene bis(cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane Hexane diisocyanate, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane (hereinafter also referred to as hydrogenated xylylene diisocyanate) or mixtures thereof, norbornane diisocyanate Other cycloaliphatic diisocyanates;

1,3,5-cyclohexanetriisocyanate, 1,3,5-cyclohexanetrimethylisocyanate, 2-(3-isocyanatopropyl)-2,5-bis(methylisocyanate base)-bicyclo(2,2,1)heptane, 2-(3-isocyanatopropyl)-2,6-bis(isocyanatomethyl)-bicyclo(2,2,1)heptane Alkane, 3-(3-isocyanatopropyl)-2,5-di(isocyanatomethyl)-bicyclo(2,2,1)heptane, 5-(2-isocyanatoethyl) Base)-2-isocyanatomethyl-3-(3-isocyanatopropyl)-bicyclo(2,2,1)heptane, 6-(2-isocyanatoethyl)-2 -Isocyanatomethyl-3-(3-isocyanatopropyl)-bicyclo(2,2,1)heptane, 5-(2-isocyanatoethyl)-2-isocyanate Methoxy-2-(3-isocyanatopropyl)-bicyclo(2,2,1)-heptane, 6-(2-isocyanatoethyl)-2-isocyanatomethyl - Alicyclic triisocyanates such as 2-(3-isocyanatopropyl)-bicyclo(2,2,1)heptane, and the like.

Examples of araliphatic polyisocyanates include:

1,3- or 1,4-xylylene diisocyanate or mixtures thereof, ω, ω'-diisocyanato-1,4-diethylbenzene, 1,3- or 1,4-bis(1 - araliphatic diisocyanates such as isocyanato-1-methylethyl)benzene (hereinafter also referred to as tetratylene xylylene diisocyanate) or mixtures thereof;

1,3,5-Aroliphatic triisocyanates such as methyl triisocyanate, benzene, etc.

Examples of aromatic polyisocyanates include:

m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4- or 4,4'-diphenylmethane diisocyanate (hereinafter also referred to as MDI ) or its mixture, 2,4- or 2,6-toluene diisocyanate (hereinafter also referred to as TDI) or its mixture, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate and other aromatic family of diisocyanates;

Triphenylmethane-4,4',4"-triisocyanate, 1,3,5-benzene triisocyanate, 2,4,6-toluene triisocyanate and other aromatic triisocyanates;

Aromatic tetraisocyanates such as 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate, etc.

In addition, examples of derivatives of the above-mentioned polyisocyanates include:

Dimer, trimer, biuret, allophanate, carbodiimide, uretdione, oxadiazinetrione, polymethylene polyphenyl polyisocyanate Isocyanate (hereinafter also referred to as crude MDI (Crude MDI) or polymeric MDI (Polymeric MDI)) and crude TDI (Crude TDI), etc.

Examples of modified products of the above-mentioned polyisocyanates include:

Make the above-mentioned polyisocyanate or polyisocyanate derivative and the following low-molecular-weight polyol or low-molecular-weight polyamine according to the ratio that makes the isocyanate group remain, that is, according to the ratio of the isocyanate group of the polyisocyanate or its derivative to the hydroxyl group of the low-molecular-weight polyol or Low molecular weight polyamines are reacted at an excess ratio of amino groups to obtain polyol-modified or polyamine-modified isocyanates.

The above-mentioned organic polyisocyanate compounds may be used alone or in combination of two or more. Among the above-mentioned organic polyisocyanate compounds, aromatic diisocyanate or polymeric MDI is preferred, and polymeric MDI is more preferred in consideration of the working environment and ease of handling during handling.

In the present invention, the second agent is preferably composed of only organic polyisocyanate compounds, but the second agent may contain other components such as solvents, dispersion media, and additives as necessary. Examples of other components include UV absorbers, antioxidants, plasticizers, silane coupling agents, metal catalysts, waterproofing agents, defoamers, curing accelerators, mold release agents, mold release aids, tackifiers, Formaldehyde trapping agent, crosslinking agent, stabilizer, etc. Other components are not particularly limited, but can be used in a molar ratio of 5 parts by weight or less with respect to 100 parts by weight of the organic polyisocyanate-based compound as the amount used.

"Binder"

In the present invention, the so-called adhesive includes both adhesives and binders.

The adhesive of the present invention is composed of the above-mentioned first agent and the second agent, the weight ratio of the active ingredients of the second agent to the first agent, that is, the organic isocyanate compound in the second agent, and the organic isocyanate compound in the first agent. The weight ratio of the total weight of the polyol (a) having a nitrogen atom weight average molecular weight of 150 to 4000 and the compound (b) having a nitrogen atom is preferably in the range of 100:2 to 35 from the viewpoint of adhesiveness and reactivity It is considered that it is preferably used in an amount satisfying 100:5 to 25 (second dose: first dose). With respect to 100 parts by weight of the active ingredient of the second agent, when the usage amount of the first agent is less than 2 parts by weight, the curing time sometimes has no change compared with the existing curing time, and there is no effect of improving productivity. Aspects and operability all cause waste. When the amount of the first agent exceeds 35 parts by weight, the curing reaction of the adhesive usually proceeds, so it is difficult to obtain the physical strength of the prepared composite material.

In addition, in the binder, the usage amount of the solid content of the second agent is in the range of 2 to 30%, preferably 3%, relative to the sufficient dry weight of the raw materials for composite materials such as inorganic materials and/or lignocellulose materials. ~20% range. Within this range, a composite material excellent in productivity, secondary processability, water resistance, bending strength, and peeling strength can be obtained.

<curing time of adhesive>

The adhesive of the present invention is characterized in that the curing time [seconds at 60° C.] measured according to the gelation time test method (A method) of JIS K6807 using at least one mixture obtained by the first agent and the second agent ] (denoted as T ₆₀ ) divided by the similarly measured curing time at 110°C [sec] (denoted as T ₁₁₀ ) (T ₆₀ /T ₁₁₀ ) is 30 or more, preferably 31 or more, and more It is preferably 33 or more, and the curing time at 60° C. is 1 hour or more, preferably 1.2 hours or more, more preferably 1.5 hours or more. That is, in the adhesive of the present invention, the total amount of (a) and (b) in the first agent is at least 2 to 20 parts by weight relative to 100 parts by weight of the organic isocyanate compound in the second agent. When adjusting the mixture of the first agent and the second agent in a certain amount ratio, _T60 and _T110 should just satisfy the above-mentioned range. In the adhesive of the present invention, it is preferable to use the first agent and the second agent in an amount ratio of T ₆₀ to T ₁₁₀ satisfying the above-mentioned range.

In particular, when the above-mentioned first agent and second agent have the desired composition, since the curing time [second] (T ₆₀ ) at 60° C. is increased, the stacking tolerance is excellent and the handleability is excellent. When the numerical value (T ₆₀ /T ₁₁₀ ) and the curing time are the above values, an adhesive having excellent productivity can be obtained due to the short curing time at high temperature due to the stacking tolerance. Therefore, it can be used as a binder for inorganic materials and/or lignocellulosic materials. In particular, it has excellent bulk tolerance and short curing time at high temperature. It is preferably used for compression molding.

It should be noted that the solidification time of the mixture obtained by mixing and stirring the first agent and the second agent was measured according to method A, and the measuring instruments and measuring methods required for the measurement will be described in detail below.

[measuring instrument]

A constant temperature bath (oil bath) capable of maintaining the temperature of the solution at 60°C±1°C and 110°C±1°C was used as a measuring instrument required for the measurement. When measuring at 60° C., a glass stirring rod with a diameter of 4 mm and a length of about 30 cm was used, and when measuring at 110° C., a glass stirring rod with a diameter of 3 mm and a length of about 30 cm was used. In addition, the test tube is 18×165mm specified in JIS R3503. The temperature of the constant temperature bath was measured using a thermometer at 100°C and 200°C specified in JIS B7411. The sample was weighed using a balance manufactured by Sartorius Corporation with a product number of CP4202-S, and a balance with a reciprocal sensitivity of 100 mg or less was used.

[Measuring method of curing time]

Weigh 100g of the second dose and the specified amount of the first dose into an appropriate container, mix thoroughly, take 2g of it and put it into the test tube, add a stirring rod, and test it in a constant temperature bath kept at 60°C±1°C. The time when the sample surface is immersed to about 2cm below the bath liquid surface is taken as the start time. Stir the sample occasionally and measure the time until the stir bar becomes immovable and fully cured. It should be noted that this test was performed more than two times, and the average time was expressed in seconds as the curing time of the sample.

In addition, measure the gelation time at 110°C in the same way, weigh 100g of the second agent and a specified amount of the first agent into an appropriate container, mix well, take 2g of them into the test tube, add a stirring rod, The time when the sample surface is immersed in a constant temperature bath kept at 110 °C ± 1 °C to about 2 cm below the bath liquid level is taken as the start time. Stirring of the sample is continued and the time until the stir bar becomes immovable and fully cured is measured. It should be noted that this test was performed two or more times, and the average time was expressed in seconds as the curing time of the sample.

According to JIS K6807, the curing time of the mixture obtained by mixing and stirring 2 to 35 parts by weight of the first part relative to 100 parts by weight of the second part at 60°C and 110°C was measured using the above-mentioned curing time measurement method.

<How to use the adhesive>

The method of using the adhesive of the present invention is not particularly limited, and the adhesive may be obtained by uniformly mixing the second agent and the first agent in advance, or may be used separately.

In addition, the binders may be separately coated or dispersed in the inorganic material and/or lignocellulosic material as a raw material for composite materials, or may be mixed and used before coating or dispersing, considering productivity and workability. When waiting, the method of separately applying or dispersing the first agent and the second agent is preferable. Various methods can be used for coating or dispersing, and there is no particular limitation as long as it can be uniformly coated or dispersed in the inorganic material and/or lignocellulose material of the composite material raw material using a sprayer or the like.

The ratio of the binder and the inorganic material and/or the lignocellulose material used as the raw material for the composite material is that the second agent as an active ingredient in the binder and the lignocellulose material or the inorganic material used as the raw material for the composite material The completely dry weight ratio is in the range of 2:100 to 30:100 (second agent: lignocellulose material or inorganic material as a raw material for composite materials), preferably in the range of 3:100 to 20:100. When the second agent is less than 2 parts by weight with respect to 100 parts by weight of the inorganic material and/or lignocellulose material of the raw material for the composite material, there is a tendency that it is difficult to obtain the effect as a binder. Due to the physical properties of the composite material, even if the binder is used in an amount exceeding 30 parts by weight, it is costly and industrially wasteful.

It should be noted that, among the adhesives of the present invention, formaldehyde adhesives, epoxy adhesives, acrylic adhesives, synthetic rubber adhesives, and vinyl acetate adhesives can be used simultaneously. . These binders may be used alone or in combination of two or more.

Examples of formaldehyde-based binders include urea resins, melamine resins, urea-melamine resins, melamine-urea resins, phenol resins, phenolic melamine resins, and melamine-phenolic resins.

As an epoxy-type adhesive, the following one-component type adhesive obtained by hardening using a main ingredient etc. are mentioned, for example. The main agent is epichlorohydrin bisphenol A type resin, epichlorohydrin bisphenol F type resin, epoxy resin with methyl epichlorohydrin as matrix, chain Shaped epoxy resin, polyalkylene ether epoxy resin, novolac epoxy resin, cycloaliphatic epoxy resin, etc. The curing is the curing of organic polyamines such as aliphatic simple amines, internal amine adducts, separation adducts, polyamide resins, aromatic amines, amine precondensates, amine salts, etc., and organic acid anhydrides, etc. Curing, amino and phenolic resin combined curing, curing by esterification with fatty acid, curing by alkyd resin modification, curing by curing agent such as amino and thiol, curing by latent curing agent, as the latent Examples of the permanent curing agent include hydrazine and other curing agents that are solid at room temperature and liquefy when heated.

As an acrylic adhesive, for example, an emulsion obtained from:

Examples of aromatic vinyl-based monomers include styrene, α-methylstyrene, divinylbenzene, and the like;

Examples of unsaturated carboxylate monomers include methyl methacrylate, ethyl acrylate, isobutyl methacrylate, tert-butyl methacrylate, vinyl acetate, acrylonitrile, isobutyl acrylate, n-butyl acrylate, Butyl, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate and other acrylates or methacrylates having an alkyl group with 4 to 12 carbon atoms, and as Acrylic monomers having amide groups include acrylamide, methacrylamide, maleimide, N-methylolacrylamide, N-methylolmethacrylamide, N-(methoxymethyl base) acrylamide, N-(isopropoxymethyl)acrylamide, N-(butoxymethyl)acrylamide, N-(isobutoxymethyl)acrylamide, N-(octyloxymethyl)acrylamide base) acrylamide, N-carboxymethylacrylamide, etc.;

Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, and crotonic acid as monocarboxylic acids, and itaconic acid, maleic acid, and fumaric acid as dicarboxylic acids.

Examples of synthetic rubber-based adhesives include emulsions using butadiene and the following substances as raw materials:

Examples of aromatic vinyl-based monomers include styrene, α-methylstyrene, divinylbenzene, and the like;

Examples of unsaturated carboxylate monomers include methyl methacrylate, ethyl acrylate, isobutyl methacrylate, t-butyl methacrylate, vinyl acetate, acrylonitrile, isobutyl acrylate, n-butyl acrylate acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate and other acrylates or methacrylates with alkyl groups with 4 to 12 carbon atoms;

Acrylamide, methacrylamide, maleimide, N-methylolacrylamide, N-methylolmethacrylamide, N-(methoxymethacrylamide, base) acrylamide, N-(isopropoxymethyl)acrylamide, N-(butoxymethyl)acrylamide, N-(isobutoxymethyl)acrylamide, N-(octyloxymethyl)acrylamide base) acrylamide, N-carboxymethylacrylamide, etc.;

Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, and crotonic acid as monocarboxylic acids, and itaconic acid, maleic acid, and fumaric acid as dicarboxylic acids.

Examples of vinyl acetate-based adhesives include adhesives obtained by polymerizing protective colloids using vinyl acetate monomers as a main raw material and monomers described in the above-mentioned acrylic adhesives as raw materials.

In addition, the binder of the present invention may be used in combination with a conventional formaldehyde-based binder, or may be used using construction waste materials or the like. In this case, the amount of formaldehyde released from the composite is non-zero. Therefore, in order to reduce the amount of formaldehyde at this time, it is effective to add a formaldehyde trapping agent to the surface layer and/or the core layer. As the formaldehyde trapping agent, any substance may be used as long as it reacts with formaldehyde, and examples thereof include ammonium salts of acids, sulfites of alkali metals, and the like. Among them, those having an amino group, such as urea, guanyl urea, melamine, ammonia, etc., are preferable. As the method of addition, as long as the formaldehyde scavenger exists in the composite material when the composite material is produced, it can be added to the binder, or it can be added to the material component before drying or the material component when the binder is applied. to mix.

Furthermore, the above-mentioned formaldehyde trapping agent is dissolved in water, and after the composite material is thermocompressed, it is applied or sprayed for use.

"Composite Materials"

The adhesive of the present invention can be suitable for the bonding of inorganic materials and/or lignocellulosic materials. Therefore, by coating or dispersing binders in inorganic materials and/or lignocellulosic materials by various methods, and bonding them by thermocompression molding, productivity, adhesion, water resistance, Composite material with excellent dimensional stability and secondary processability. As the above-mentioned composite material, it is composed of one or more raw materials of the following inorganic materials and/or lignocellulose materials, such as particleboard, waffle board, fiberboard, OSB, rice straw board, straw board, rice A shell plate, a plate in which an inorganic material is mixed with the above-mentioned plate material, and an inorganic plate.

Inorganic materials and/or lignocellulosic materials may be in the form of chips, plates, strips, thin slices, finely pulverized powders, or fibers, or a mixture thereof . Examples of inorganic materials include brown asbestos; perlite; porous perlite or vermiculite obtained by heating and foaming obsidian, vermiculite, and deposits of volcanic ash and sand. Stone (vermiculite), foamed white sand accumulation layer; glass ball (Glass Balloon) and white sand accumulation layer ball of tiny hollow body formed by using glass, alumina, floating dust, silica sand, tribute rock, etc. as raw materials; calcium carbonate, aluminum hydroxide wait. In order to obtain a lightweight molded article, the bulk density of the inorganic foam-containing particles is preferably 0.3 g/cm ³ or less. The inorganic foam-containing particles may be subjected to surface treatment using a silane coupling agent or the like in order to improve the adhesiveness with the binder.

On the other hand, as the lignocellulose material, for example, chipboard, and OSB (oriented strand board), waffle board, and LSL (laminated wood laminated wood) used as wood chip strips ( Strand chips), wood chips (dust chips), flake chips (flake chips), and fibers used in hard boards, MDF, insulation boards, and agricultural products such as sorghum stalks, bagasse, rice husks, rice straw, and wheat straw. These raw materials may be used alone or in combination of two or more.

In addition, the board obtained by using inorganic materials and/or lignocellulose materials as raw materials is not particularly limited, and examples include a one-layer structure, a three-layer structure consisting of a surface layer/core layer/surface layer structure, or a board composed of A multi-layer structure consisting of two or more surface layers/more than two core layers/more than two surface layers. Furthermore, it is also possible to have random multilayers like a mixture of inorganic material and lignocellulose material, or lignocellulose material/inorganic material/lignocellulose material, or inorganic material/lignocellulose material/inorganic material. structure.

"Manufacturing method of composite materials"

An example of the production method of the composite material of the present invention is given below.

The manufacturing method of the composite material is the same as the manufacturing method of a general board, and there are a wet method and a dry method, and it is not specifically limited.

A method of manufacturing a single-layer composite material using a dry method will be described in detail below.

Predetermined amounts of organic isocyanate compound, curing accelerator composition, and internal release agent are attached to the raw material for composite material. As the attachment method, conventionally known methods in board production, for example, methods such as spraying with a sprayer or the like can be used.

The raw material for the composite material to which the above-mentioned adhesive is attached is molded on a caul plate coated with an external release agent as needed, and pre-pressed as needed to form a mat, which is then hot-pressed molding, the composite material of the present invention can be obtained. It should be noted that an external mold release agent is applied in advance as necessary on the presser during thermocompression molding. Usually, pre-pressing is preferably carried out at a pressure of 0.2-1.5 MPa for 10-30 seconds, and hot press molding is preferably carried out at a pressure of usually 0.5-7.0 MPa and a temperature of 90-220°C for 5-30 seconds/mm.

The method of manufacturing the three-layer composite material using the dry method will be described in detail below.

A predetermined amount of an organic isocyanate compound, a curing accelerator composition, and an internal mold release agent are attached to the raw material for a composite material for a surface layer. On the other hand, predetermined amounts of the organic isocyanate compound and the curing accelerator composition are attached to the raw material for the composite material for the core layer. As the above-mentioned adhesion method, conventionally known methods in board production, for example, methods such as spraying with a sprayer or the like can be used.

The raw material for the composite material for the surface layer to which the above-mentioned adhesive is attached is molded on a base plate coated with an external mold release agent in advance if necessary, and then the raw material for the composite material for the core layer to which the above-mentioned adhesive is attached and the raw material for the composite material to which the above-mentioned adhesive is attached. The raw materials for the composite material for the surface layer of the adhesive are laminated in this order, and pre-pressed as necessary to form a slab consisting of the surface layer/core layer/surface layer, which is hot-press-molded to obtain the composite material of the present invention. It should be noted that an external mold release agent is applied in advance as necessary on the presser during thermocompression molding. Usually, pre-pressing is preferably carried out at a pressure of 0.2-1.5 MPa for 10-30 seconds, and hot press molding is preferably carried out at a pressure of usually 0.5-7.0 MPa and a temperature of 90-220°C for 5-30 seconds/mm.

The adhesive of the present invention does not react during the accumulation of raw materials for composite materials after the adhesive is applied, and on the other hand, has rapid curing properties during thermocompression molding, so the curing of the adhesive can be easily adjusted time. Therefore, since it is easy to adjust the hot press molding time, especially by using it for inorganic materials and lignocellulose materials, it is possible to provide improved productivity of composite materials such as boards, secondary processability of finished products, water absorption expansion rate, bending High-quality composite material with excellent elastic modulus and peel strength. In the step of hot press molding, the temperature is in the range of 90 to 220°C, preferably 110 to 220°C, more preferably 120 to 200°C. When it is higher than the lower limit, the curability of the composite material during hot pressing is excellent, and when it is lower than the upper limit, the hot press formability and the surface properties of the composite material after hot press molding are excellent.

<Release agent>

In the manufacturing method of the composite material of this invention, a mold release agent can be used as needed.

The release agent is not particularly limited, and examples thereof include silicon-based, fluorine-based, carnauba wax-based, montan wax-based, paraffin-based, and polyethylene-based. Among these, polyethylenes and carnauba waxes are preferable from the viewpoint of secondary processability of the resulting composite material. The above-mentioned release agent can be used as an internal release agent, added as a binder system to the interior of inorganic materials and/or lignocellulose materials, etc., which are raw materials for composite materials, and used, and can also be used as an external release agent, Apply to the surface of the press, the backing plate, the front and back of the slab of the inorganic material and/or lignocellulose material used as a raw material for composite materials, and the steel belt, etc., using hot press molding equipment. The combination of the internal release agent and the external release agent is not particularly limited, and each can be independently selected from the release agents exemplified above.

The added amount of the internal release agent is preferably 0.1 to 1.0% by weight based on the total dry weight of the inorganic material and/or lignocellulose material. Furthermore, it is more preferable to add 0.2 to 0.7 weight%. If the amount of the internal mold release agent added is too small, sufficient mold release properties cannot be obtained, and if it exceeds 1.0% by weight, it is uneconomical. When secondary processing of composite materials obtained from inorganic materials and/or lignocellulose materials Excellent adhesion and physical strength of secondary processed products are difficult to obtain.

Spraying or coating an external mold release agent on the surface of a press, backing plate, inorganic material and/or lignocellulosic material used as a raw material for composite materials, the front and back of a slab, steel belt, etc. The amount is usually 5 to 150 g, more preferably 10 to 100 g per 1 m ² . The external mold release agent is also the same as the internal mold release agent. If the amount of spraying and coating is small, good mold release properties cannot be obtained. Adhesion and physical strength of secondary processed products are difficult to obtain.

In addition, in the manufacture of composite materials, ultraviolet absorbers, antioxidants, plasticizers, silane coupling agents, Metal catalysts, waterproofing agents, defoamers, release aids, tackifiers, formaldehyde traps, crosslinking agents, stabilizers, etc.

[Example]

The following examples are given to further describe the present invention in detail, but the present invention is not limited to these examples. In addition, parts and % in examples are based on weight unless otherwise indicated.

"Production Examples 1 to 8: (a) Polyhydric Alcohols Not Having Nitrogen Atoms"

As shown in the following production examples 1-8, the polyether polyol which does not have a nitrogen atom, and the polyester polyol which does not have a nitrogen atom were produced, and the weight average molecular weight of the obtained polyol (a) was measured, and it shows respectively.

<Manufacturing example 1>

Propylene oxide and ethylene oxide were added to ethylene glycol at a molar ratio of 2:3 to obtain a polyether polyol with a weight average molecular weight of 150.

<Manufacturing example 2>

Propylene oxide was added to glycerol to obtain a polyether polyol with a weight average molecular weight of 1,500.

<Manufacturing example 3>

Propylene oxide and ethylene oxide were added to pentaerythritol at a molar ratio of 3:2 to obtain a polyether polyol with a weight average molecular weight of 3,000.

<Manufacturing example 4>

Propylene oxide and ethylene oxide were added to sorbitol at a molar ratio of 2:3 to obtain a polyether polyol with a weight average molecular weight of 4,000.

<Manufacturing example 5>

A polyester polyol having a weight average molecular weight of 150 was obtained from isophthalic acid and ethylene glycol.

<Manufacturing example 6>

A polyester polyol having a weight average molecular weight of 2900 was obtained from an adduct of bisphenol A with an average of 3 moles of propylene oxide and succinic acid.

<Manufacturing example 7>

A polyester polyol having a weight average molecular weight of 4000 was obtained from an adduct of bisphenol A with an average of 4 moles of ethylene oxide and adipic acid.

<Manufacturing example 8>

A polyester polyol having a weight average molecular weight of 6,000 was obtained from an adduct of bisphenol A with an average of 3 moles of propylene oxide and succinic acid.

"Production Examples 9-16: (b) Compounds Having Nitrogen Atoms"

As shown in the following Production Examples 9 to 16, polyether polyols having nitrogen atoms and polyester polyols (b-1) having nitrogen atoms among compounds having nitrogen atoms (b) were produced, and the obtained polyols (b-1) were measured. The weight-average molecular weights of -1) are shown respectively.

<Manufacturing example 9>

Ethylene oxide was added to aniline to obtain a polyether polyol with a weight average molecular weight of 270.

<Manufacturing Example 10>

Propylene oxide and ethylene oxide were added to diethylenetriamine at a molar ratio of 3:2 to obtain a polyether polyol with a weight average molecular weight of 1,500.

<Manufacturing example 11>

In o-toluenediamine, propylene oxide and ethylene oxide were added at a molar ratio of 2:3 to obtain a polyether polyol with a weight average molecular weight of 4,000.

<Manufacturing example 12>

Ethylene glycol and maleic acid were added to ethylenediamine to obtain a polyester polyol with a weight average molecular weight of 400.

<Manufacturing example 13>

Diethylene glycol and adipic acid were added to aniline to obtain a polyester polyol with a weight average molecular weight of 4000.

<Manufacturing example 14>

Propylene oxide and ethylene oxide were added in a molar ratio of 3:2 to polymethyl polyphenyl polyamine to obtain a polyether polyol with a molecular weight of 4,000.

<Manufacturing example 15>

Ethylene oxide was added to ethylenediamine to obtain a polyether polyol with a weight average molecular weight of 130.

<Manufacturing example 16>

Add propylene glycol and fumaric acid to aniline to obtain a polyester polyol with a weight average molecular weight of 6000.

[Embodiments 1 to 6]

The polyether polyol not having a nitrogen atom and/or the polyester polyol (a) not having a nitrogen atom (Manufacture Examples 1 to 7) obtained in the above-mentioned production examples and the polyether polyol having a nitrogen atom and/or The polyester polyol (b-1) (manufacture examples 9-14) which has a nitrogen atom, and the amine compound (b-2) were mixed in the ratio of Table 1, and the 1st agent was obtained. In addition, the first part by weight shown in Table 1 and 100 parts by weight of the second part were mixed and stirred, and the curing time of the obtained mixture was measured twice at 60° C. and 110° C. according to JIS K6807, and the average values are shown in Table 1. . In addition, the value (T ₆₀ /T ₁₁₀ ) obtained by dividing the curing time [second] at 60°C by the curing time [second] at 110°C is shown in Table 1 (see above for the method of measuring the curing time). In addition, the composition ratio of each component of Examples 1-6 is shown in Table 1.

[Comparative examples 1 to 4]

Similar to Table 1, the composition ratios and measurement results of the components in Comparative Examples 1 to 5 are shown in Table 2.

The description of raw materials in Tables 1 and 2 can refer to the following description.

Amine compound (b-2):

TEA: Triethanolamine

DMAEE: bis(dimethylaminoethyl) ether

TAP: Tris(dimethylaminomethyl)phenol

PEHA: Pentaethylenehexamine

PMDETA: 1,5-Pentylenediethylenetriamine

The second agent (organic isocyanate compound):

PlyM-S180: Mitsui Chemicals Polyurethane Co., Ltd. product name: Cosmonate PlyM-S180 aromatic polyisocyanate (polymeric MDI)

PlyM-120F: manufactured by Mitsui Chemicals Polyurethane Co., Ltd., brand name: Cosmonate PlyM-120F aromatic polyisocyanate (polymeric MDI)

PlyM-130F: manufactured by Mitsui Chemicals Polyurethane Co., Ltd., trade name: Cosmonate PlyM-130F aromatic polyisocyanate (polymeric MDI)

Polyols (a) having no nitrogen atoms:

PG: propylene glycol

EG: ethylene glycol

[Table 1]

[Table 2]

[Example 7: Fabrication of Composite Material]

Weigh the following amount of distilled water into the mixer, the amount of distilled water is 12% of the total weight of distilled water relative to the weight of the completely dried strip-like chips, the weight of the second dose and the weight of the first dose. The amount obtained by subtracting the amount of 3% of water contained in the flake chips from the weight of the amount of water in %. Stirring was performed at a rotation speed of 6000 per minute using a homogenizer manufactured by Tokukuki Kagaku Kogyo Co., Ltd. Slowly add the first agent (the same composition as in Example 1; 5 parts by weight relative to 100 parts by weight of the second agent added later) while stirring to make it uniformly dispersed, and then slowly add the complete The weight of the dry flaky chips is the release agent [trade name: MK-56 (carnauba wax release agent)] [Mitsui Chemicals Polyurethane Co., Ltd. system] in an amount of 0.5% by weight in terms of active ingredients, to spread evenly. Then, slowly add the second agent (the same compound as in Example 1) in an amount of 10% (w/w) relative to the weight of the pre-weighed completely dry strip-shaped chips, stir until uniformly dispersed, and form Adhesive mixture.

Add 4000g of pre-weighed flaky chips with a moisture content of 3% into the mixer, weigh the above-mentioned uniformly dispersed distilled water and the above-mentioned binder mixture, and spray the mixture with a spray gun while rotating the blade of the mixer to disperse evenly.

Weigh the evenly dispersed strip-like chips into two vinyl plastic bags (VINYLBAG) to make it a set density, one of which is pre-coated with the above-mentioned release agent as an external release agent. The backing plate was uniformly molded to a size of 40 cm×40 cm, and the composite material was molded by hot-pressing and pressing under the following composite material manufacturing conditions.

In addition, in order not to disperse moisture from the vinyl plastic bag, another uniformly dispersed strip-shaped chip was cured in an oven at 60°C for 1 hour, and then, similarly, the above-mentioned release agent was previously coated as the outer surface. The steel backing plate of the release agent was uniformly molded with a size of 40 cm x 40 cm, and the composite material was formed by hot pressing and pressing under the following composite material manufacturing conditions. The molded composite material was left in a well-ventilated place for one week, and the following evaluation tests were carried out, and the results are shown in Table 3.

[Example 8: Fabrication of Composite Material]

In addition to changing the number of revolutions of the homogenizer to 2000, as a mold release agent to Mitsui Chemicals Polyurethane Co., Ltd.: MK-004 (polyethylene mold release agent), used as the first agent and the second agent and examples 2 Except for the same substance, a composite material was produced in the same manner as in Example 7.

Table 3 shows the results of the following evaluation tests.

[Example 9: Fabrication of Composite Material]

In addition to changing the number of revolutions of the homogenizer to 2000, as a mold release agent to Mitsui Chemicals Polyurethane Co., Ltd.; MK-004 (polyethylene mold release agent), used as the first agent and the second agent and the embodiment 3 Except for the same substance, a composite material was produced in the same manner as in Example 7.

The following evaluation tests were performed, and the results are shown in Table 3.

[Example 10: Fabrication of Composite Material]

In addition to changing the number of revolutions of the homogenizer to 2000, as a release agent to Mitsui Chemicals Polyurethane Co., Ltd.; MK-521 (polyethylene release agent), used as the first agent and the second agent and the embodiment 4. Except for the same substance, a composite material was produced in the same manner as in Example 7.

The following evaluation tests were performed, and the results are shown in Table 3.

[Example 11: Fabrication of Composite Material]

Except changing the number of revolutions of the homogenizer to 2000, and using the same substance as in Example 5 as the first agent and the second agent, a composite material was produced in the same manner as in Example 7.

The following evaluation tests were performed, and the results are shown in Table 3.

[Example 12: Fabrication of Composite Material]

Composite materials were produced in the same manner as in Example 7, except that the number of revolutions of the homogenizer was changed to 2000, and the same materials as in Example 6 were used as the first and second doses.

The following evaluation tests were performed, and the results are shown in Table 3.

[Comparative Example 6: Production of Composite Material]

Composite materials were produced in the same manner as in Example 6, except that the number of revolutions of the homogenizer was changed to 2000, and the same materials as in Comparative Example 1 were used as the first and second doses.

The following evaluation tests were performed, and the results are shown in Table 3.

[Comparative Example 7: Production of Composite Material]

In addition to changing the number of revolutions of the homogenizer to 2000, as a mold release agent to Mitsui Chemicals Polyurethane Co., Ltd.: MK-521 (polyethylene mold release agent), as the first agent and the second agent, and the comparative example 2 Except for the same substance, a composite material was produced in the same manner as in Example 6.

The following evaluation tests were performed, and the results are shown in Table 3.

[Comparative Example 8: Production of Composite Material]

Except that the mold release agent was changed to Mitsui Chemicals Polyurethane Co., Ltd.; MK-521 (polyethylene mold release agent), and the same material as Comparative Example 3 was used as the first agent and the second agent, according to the embodiment 6 The same method is used to make composite materials.

The following evaluation tests were performed, and the results are shown in Table 3.

[Comparative Example 9]

In addition to changing the number of revolutions of the homogenizer to 2000, as a mold release agent to Mitsui Chemicals Polyurethane Co., Ltd.: MK-521 (polyethylene mold release agent), as the first agent and the second agent, and the comparative example Except for the same substance as in Example 5, a composite material was produced in the same manner as in Example 6.

The following evaluation tests were performed, and the results are shown in Table 3.

"Manufacturing Conditions of Composite Materials"

Raw material: flake chips (moisture content 3%)

Composite structure: one layer

Set thickness: 15mm

Set density: 750Kg/m ³

Set slab moisture content: 12%

Hot pressing temperature: 190°C

Compression pressure: 40Kgf/cm ²

Pressurization time: 3 minutes and 30 seconds

Coating amount of the solid content of the second agent in the adhesive: 10% relative to the completely dried flakes

"Evaluation Test"

The composite materials molded in Examples 7 to 12 and Comparative Examples 6 to 9 were evaluated in accordance with the test items of "particle composite materials" in JIS A5908, and the results are shown in Table 3.

<1. Bending strength>

The samples obtained in Examples 7 to 12 and Comparative Examples 6 to 9 were cut into widths of 50 mm and lengths of 275 mm (pitch of 225 mm), and bending strength tests were performed on the test pieces. The result was expressed as "normal bending strength (N/mm ² )".

<2. Wet flexural strength (B test)>

Cut the above sample in the same way as <1. Bending strength>. Then, after immersing this test piece in boiling water for 2 hours, and immersing in normal temperature water for 1 hour, the flexural strength test was performed in the soaked state. The results are expressed as "wet B flexural strength (N/mm ² )".

<3. Center peel strength test>

The samples obtained in Examples 7 to 12 and Comparative Examples 6 to 9 were cut into 50 mm×50 mm, and the center peel strength test was performed on the test pieces. The results are expressed as "central peel strength (N/mm ² )".

<4.20℃ water absorption thickness expansion rate>

The samples obtained in Examples 7 to 12 and Comparative Examples 6 to 9 were cut into 50 mm×50 mm, and the test pieces were immersed in water at 20° C. for 24 hours to conduct a water absorption thickness expansion coefficient test. The results are expressed as "20°C water absorption thickness expansion ratio (%)".

<5. Comprehensive judgment>

For evaluation tests 1 to 4, a comprehensive judgment of compliance is given based on the JIS compliance criteria of JIS A5908.

A: Conforms to JIS standard

B: Does not conform to JIS standards

Claims (9)

1. An adhesive, characterized in that, The adhesive is composed of the first agent and the second agent, The first agent contains 100 parts by weight of a polyol (a) having a weight average molecular weight of 150 to 4000 without a nitrogen atom and 0.5 to 65 parts by weight of a polyol (a) having a nitrogen atom relative to 100 parts by weight of the polyol (a). compound (b), The second agent contains organic isocyanate compounds; And the first agent and the second agent are used in such an amount that the total of (a) and (b) in the first agent is 2 to 35 parts by weight relative to 100 parts by weight of the organic isocyanate compound in the second agent And the obtained at least one mixture is obtained by dividing the solidification time obtained at 60°C according to the gelation time test method (A method) of JIS K6807 by the solidification time obtained according to the gelation time test method (A method) of JIS K6807. The curing time at 110° C. gave a value of 30 or more, and the curing time at 60° C. was 1 hour or more. 2. The adhesive according to claim 1, wherein the first agent consists of only 100 parts by weight of polyol (a) having a weight average molecular weight of 150-4000 without nitrogen atoms and 100 parts by weight of The polyol (a) is composed of 0.5 to 65 parts by weight of the compound (b) having a nitrogen atom. 3. The adhesive according to claim 1 or 2, wherein the second agent consists only of organic isocyanate compounds. 4. The adhesive according to any one of claims 1 to 3, characterized in that: In the first dose, Described (a) is the polyether polyol that does not contain nitrogen atom and/or the polyester polyol that does not contain nitrogen atom, The (b) is composed of a polyether polyol having a nitrogen atom and/or a polyester polyol (b-1) having a nitrogen atom and an amine compound (b-2), containing 0 to 100 parts by weight of (a). ~50 parts by weight (b-1) and 0.5~15.0 parts by weight (b-2). 5. A composite material, characterized in that it is obtained by thermocompression molding a mixture containing the binder according to any one of claims 1 to 4 and inorganic materials and/or lignocellulose materials . 6. A method for producing a composite material, characterized in that the binder according to any one of claims 1 to 4 is mixed with an inorganic material and/or a lignocellulose material, and subjected to thermocompression molding. 7. The method for producing a composite material according to claim 6, further comprising using a release agent. 8. The manufacturing method of the composite material according to claim 6 or 7, characterized in that the temperature of hot pressing is in the range of 90-220°C. 9. The method for producing a composite material according to any one of claims 6 to 8, characterized in that the inorganic material and/or lignocellulose material is in the form of chips, plates, strips, thin slices shape, finely pulverized powder or fiber, or their mixed form.